Substituted polythiophenes, processes for their preparation...

Details Substituted polythiophenes, processes for their preparation... Substituted polythiophenes, processes for their preparation...

1999-01-08

2001-06-05

Truong, Duc (Department: 1711)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

From sulfur-containing reactant

C528S373000, C528S485000, C540S001000, C548S117000, C427S407100

Reexamination Certificate

active

06242561

ABSTRACT:

The present invention relates to a polythiophene, comprising structural units of the general formulae (I) and (II)
where X and Y independently of one another can be identical or different and are a linear or branched-chain C
1
- to C
22
-alkyl group; a linear or branched-chain C
1
- to C
22
-alkoxy group; a linear or branched-chain C
1
- to C
22
-alkoxyalkyl group; a linear or branched-chain C
1
- to C
22
-acyl group; a linear or branched-chain C
1
- to C
22
-thioacyl group; a linear or branched-chain C
1
- to C
22
-acyloxy group; a linear or branched-chain C
1
- to C
22
-thioacyloxy group; a C
5
- to C
8
-cycloalkyl group, a C
6
- to C
18
-aryl group or a C
5
- to C
8
-heterocyclic group, which in each case can in turn be substituted by one or more linear or branched-chain C
1
- to C
22
-alkyl group(s), one or more linear or branched-chain C
1
- to C
22
-alkoxy group(s), one or more linear or branched-chain C
1
- to C
22
-alkoxyalkyl group(s), one or more linear or branched-chain C
1
- to C
22
-acyl group(s) or one or more linear or branched-chain C
1
- to C
22
-thioacyl group(s); NO
2
; or NHR
1
, where R
1
may be identical or different and is hydrogen or a linear or branched-chain C
1
- to C
22
-alkyl group, a linear or branched-chain C
1
- to C
22
-alkoxy group, a linear or branched-chain C
1
- to C
22
-alkoxyalkyl group, a linear or branched-chain C
1
- to C
22
-acyl group or a linear or branched-chain C
1
- to C
22
-thioacyl group, or X and Y, together with the atoms to which they are bonded, form a carbon-containing ring system which beside carbon contains nitrogen (N), oxygen (O), sulfur (S) or phosphorus (P) heteroatoms or mixtures of two or more of these heteroatoms,
where this ring system can in turn be substituted on the carbon atom(s), the nitrogen atom(s) or the phosphorus atom(s) in each case by a group Z, where each Z independently of one another is a group as defined above for X and Y, or
two adjacent groups Z together form a radical represented by one of the following general formulae (III) to (VI)
where A is carbon (C), nitrogen (N), phosphorus (P) or mixtures of two or more of these atoms,
where, if A is carbon, each of these As can either carry a hydrogen atom or can in turn be substituted as defined above for X and Y, obtainable by the Stille reaction, wherein 2,5-dihalothiophene or 2,5-ditriflatethiophene and thiophene derivatives which are bis(trialkyltin)-substituted on the carbon atoms adjacent to the sulfur, which correspond to the structural unit (II) defined above, or 2,5 bis(trialkyltin)thiophene and thiophene derivatives which are bis(halo)- or bis(triflate)-substituted on the carbon atoms adjacent to the sulfur, which correspond to the structural unit (II) defined above, are reacted with one another in suitable solvents in the presence of suitable Pd(0) or Pd(II) complexes or salts thereof as catalyst, or the Suzuki reaction, wherein 2,5-dihalo- or 2,5-triflate-substituted thiophenes, which correspond to the structural unit (II) according to the invention, are reacted with thiophenediboric acid or thiophenediboric acid esters in the presence of a base and of a palladium complex of the structure PdL
4
(L=ligand), wherein the diboric acid (ester) derivatives of the thiophene derivatives corresponding to the above structural units (II) are reacted with 2,5-dihalo- or 2,5-triflate-substituted thiophene in the presence of a base and a palladium complex, as defined above.
It further relates to processes and monomers for their preparation, to their use in various industrial fields, and to an electrically conductive material which contains at least one polythiophene according to the invention.
Polythiophenes are an important class of conjugated polymers having high electrical conductivity and nonlinear optical properties and can be used as materials for semiconductors (see, inter alia, EP-B-0 332 704 and P. N. Prasad, D. J. Williams “Introduction to NLO effects in molecules and polymers”, John Wiley and Sons, Inc. (1991)). The polythiophenes furthermore have electrochromic and antistatic properties (see N. Arsalani and K. E. Geckeler “Conducting isopolymers: preparation, properties, and applications”, J. Prakt. Chem. 337 (1995, pp. 1-11)).
Until now, almost exclusively homopolymers of thiophene or substituted thiophenes were known. In this case, usually only simple 3-alkyl- or 3,4-dialkylthiophenes were polymerized and investigated with respect to possible industrial applications. A review of the polythiophenes prepared to date and the most frequently used processes for their preparation is given by Hans R. Kricheldorf “Handbook of polymer synthesis”, Part B, pp. 1383-1390 (1992), M. Pomerantz “Processable polymers and copolymers of 3-alkylthiophenes and their blends”, Synthetic Metals, 41-43 (1991), pp. 825-830, and EP-A-0 339 340.
The J 60 120 722 relates to linear copolymers comprising 5-membered heterocyclic compounds having functional groups being selected among halogen, hydroxy, amino or carbohydrate groups, as defined therein. These copolymers are produced by anodic oxidation.
The JP 63 344 578 relates to the preparation of an electrically conductive polymer being constituted of 3,4-substituted heterocyclic 5-membered ring compounds, by means of a polymerization in the presence of an oxidizing agent, such as iron chloride, in an organic solvent.
&agr;-Stannylthiophen of formula (n-butyl)
3
Sn(C
4
H
2
S)
3
—Sn(n-butyl)
3
is disclosed in J.Org.Chem. 1995, 60, pp. 6813-6819.
2,5-Dibromo-3,4-diacetaminothiophene and its preparation is disclosed in “Bulletin de la Société Chimique de France, 1986, no. 2, pp. 267-275”.
The “Bulletin de la Société Chimique de France, 198 3, no. 5-6, pp. II 159-II 163” discloses non-substituted Thieno [3,4-b]pyrazine as well as the in 2- or 3- or in 2- and 3-position by a methyl group substituted derivative thereof, as well as their preparation.
Soluble poly(2,3-dihexylthieno[3,4-b]pyrazines) were prepared by M. Pomerantz et al. by iron chloride/oxygen polymerization of the corresponding monomers (see M. M. Pomerantz “New processable low band-gap, conjugated polyheterocycles”, Synthetic Metals, 55-57, pp. 960-965 (1993), and J. Chem. Soc. Commun. 1992, pp. 1672-73). By means of this process, only doped substances can be prepared. Even after treatment with aqueous ammonia or hydrazine, an EPR signal and line widening in the NMR spectra were observed, which points to the presence of paramagnetic species.
As processes for their preparation, until now mainly chemical (e.g. by means of FeCl
3
) or electrochemical oxidation of a single precursor or of a mixture of two different 3-alkylthiophenes (see M. Pomerantz “Processable polymers and copolymers of 3-alkylthiophenes and their blends” Synthetic Metals, 41-43 (1991), pp. 825-830, in particular p. 828, and M. Berggren et al. “Light-emitting diodes with variable colours from polymer blends”, Nature 372 (1994), pp. 444-446, in particular p. 444), were carried out with formation of the corresponding polymers linked in the 2,5-position.
A further, general starting point for the preparation of oligo- or polythiophenes includes the catalytic coupling of organometallic reagents (usually Grignard reagents) (see Kricheldorf, loc. sit.).
It is to be taken into account here, however, that thiophenes with functional groups, such as, for example, nitro, carbonyl, imino, amido, nitrile, pyridine and pyrazine groups, cannot be employed in this process.
A relatively new process for the preparation of new C—C linkages is the Stille reaction. According to this reaction, an organic electrophile is reacted with an organotin reagent in the presence of a suitable solvent and of a Pd(0) or Pd(II) complex (see J. K. Stille “The palladium-catalyzed cross-coupling reactions of organotin reagents with organic electrophiles”, Angew. Chem. Int. Ed. Engl. 25, pp. 508-542 (1986)). This reaction has already been successfully carried out for the preparation of poly(2,5-thieno-1,4-phenylenes) according to the following scheme (see Z. Bao et al., J. Am. Chem. Soc., 117, 12426-1

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